TW201805347A - Thermal transfer sheet and combination of transfer foil and thermal transfer sheet - Google Patents

Abstract

To provide: a thermal transfer sheet from which a transfer layer is able to be accurately removed; and a combination of a transfer foil and a thermal transfer sheet. A thermal transfer sheet 10 which has a peel-off layer 4 provided on a base 1, and which is configured such that (i) the peel-off layer 4 contains at least a vinyl chloride resin and an acrylic resin, and the mass of the vinyl chloride resin relative to the total mass of the peel-off layer 4 is more than 50% by mass but 95% by mass or less, or (ii) the peel-off layer 4 contains a polyester resin that has a number average molecular weight (Mn) of 17,000 or less and a glass transition temperature (Tg) of from 50 DEG C to 120 DEG C (inclusive).

Description

Thermal transfer sheet, and combination of transfer foil and thermal transfer sheet

The present invention relates to a thermal transfer sheet and a combination of a transfer foil and a thermal transfer sheet.

As proposed in Patent Document 1, as a means for forming a photocopy on an object to be transferred without restriction, a transfer layer (hereinafter, sometimes referred to as a transfer layer) including a receiving layer that is releasably provided on a substrate is used. ) Intermediate transfer media. According to the intermediate transfer medium, a thermal transfer sheet having a color material layer is used to form a thermal transfer image on the receiving layer of the intermediate transfer medium, and then the transfer layer containing the receiving layer is transferred to an arbitrary layer. A photocopy of a thermal transfer image can be obtained on any transferee. In particular, the intermediate transfer medium is particularly preferably used for a transfer body in which a color material is difficult to migrate and cannot directly form a high-quality image, and a transfer body that is easily fused with a color material layer during thermal transfer.

However, depending on the type of photocopying material that can be used to transfer the transfer layer of the intermediate transfer medium to the transferee, there must be an IC chip section, a magnetic pattern section, an antenna section for transmitting and receiving information, and a signature section. In some cases, there may be a defective area covered by the transfer layer on the surface of the transfer target. In other words, it may be necessary to expose the surface of the transferee. condition.

In these cases, try to use a thermal transfer sheet with a peeling layer on one side of the substrate. On the transferee, before the transfer layer of the intermediate transfer medium is transferred, The predetermined region of the removal layer for removing the transfer layer is, for example, an area of the transfer layer (sometimes referred to as peeling) where transfer of the object to be transferred is not desired. For example, in Patent Document 2, it is proposed that after the peeling layer of the thermal transfer sheet is brought into contact with the transfer layer of the intermediate transfer medium, energy is applied to the other side of the substrate of the thermal transfer sheet, and the corresponding A method of removing a specific region of a transfer layer in a region where energy is applied by removing the layer.

The thermal transfer sheet having the above-mentioned peeling layer is required to have a function of removing a specific area of the transfer layer correctly, in other words, a function of removing a specific area of a target transfer layer, but in fact, it should be A part of the transfer layer removed by the peeling layer mostly remains on the intermediate transfer medium side, and there is still room for improvement in this regard.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-80016

[Patent Document 2] Japanese Patent Laid-Open No. 2003-326865

The present invention has been completed in view of these circumstances, and its subject matter The point is to provide a thermal transfer sheet that can remove a specific area of the transfer layer correctly, and a combination of a transfer foil and a thermal transfer sheet.

The thermal transfer sheet according to the embodiment of the present disclosure for solving the above-mentioned problems is a thermal transfer sheet provided with a peeling layer on a substrate, wherein the peeling layer contains at least a vinyl chloride resin and an acrylic resin, The mass of the vinyl chloride-based resin is in a range of more than 50% by mass and less than 95% by mass with respect to the total mass of the release layer.

In addition, the thermal transfer sheet according to the embodiment of the present disclosure for solving the above-mentioned problems is a thermal transfer sheet provided with a peeling layer on a substrate, and the peeling layer contains a number average molecular weight (Mn) of 17000. Polyester resin having a glass transition temperature (Tg) of 50 ° C or higher and 120 ° C or lower.

The polyester resin may be a polyester resin having a number average molecular weight (Mn) of 3500 or more and less than 9,000. The polyester resin may be a polyester resin having a glass transition temperature (Tg) of 50 ° C to 100 ° C.

In addition, a combination of an embodiment of the present disclosure to solve the above-mentioned problems is a combination of a transfer foil and a thermal transfer sheet, characterized in that the transfer foil is provided on a support and is provided with a peelable peeling member from the support. The structure of the printed layer, the thermal transfer sheet is a structure provided with a peeling layer on the substrate, and the transfer foil and the thermal transfer sheet are overlapped so that the transfer layer and the peeling layer face each other, The transfer speed of the thermal transfer sheet is 42.3mm / sec, and the energy applied to the thermal transfer sheet is 0.143mJ / dot. The condition is that the adhesion between the transfer layer and the peeling layer measured when a specific region of the transfer layer is removed by the peeling layer is 0.03 N / cm or more.

The adhesive force measured when the energy applied to the thermal transfer sheet was changed within a range of 0.1 mJ / dot or more and 0.2 mJ / dot or less was 0.03 N / cm or more.

According to the thermal transfer sheet and the combination of the transfer foil and the thermal transfer sheet of the present invention, a specific region of the transfer layer can be accurately removed by the peeling layer.

1‧‧‧ substrate

2‧‧‧ undercoat

4‧‧‧ stripping layer

5‧‧‧ back layer

7‧‧‧ dye layer

8‧‧‧ molten layer

10‧‧‧ heat transfer sheet

16‧‧‧ heating means

30‧‧‧Intermediate transfer media (transfer foil)

31‧‧‧ transfer layer

A‧‧‧ peripheral end of transfer layer

B‧‧‧IC chip configuration area

200‧‧‧printer

201‧‧‧ Thermal transfer sheet supply means

202‧‧‧Heating means

203‧‧‧heat transfer sheet winding means

204‧‧‧Measurement method

205‧‧‧ Stripping means

FIG. 1 is a schematic cross-sectional view of a thermal transfer sheet according to an embodiment.

FIG. 2 is a schematic cross-sectional view showing a state in which a combination of a thermal transfer sheet and an intermediate transfer medium according to an embodiment is applied with energy.

FIG. 3 is a schematic cross-sectional view showing a state in which a combination of a comparative thermal transfer sheet and an intermediate transfer medium is applied with energy.

Fig. 4 is a schematic sectional view of a thermal transfer sheet according to an embodiment.

5 is a schematic plan view of an intermediate transfer medium used in combination with a thermal transfer sheet according to an embodiment.

FIG. 6 is a schematic diagram showing an example of a printer used when a transfer layer is removed by a peeling layer of a thermal transfer sheet according to an embodiment.

<< thermal transfer sheet >>

As shown in FIG. 1, a thermal transfer sheet 10 according to one embodiment of the present disclosure (hereinafter referred to as a thermal transfer sheet according to one embodiment) has a structure in which a peeling layer 4 is provided on one surface of a substrate 1. In the form shown in FIG. 1, a back layer 5 is provided on the other surface of the substrate 1, and an undercoat layer 2 is provided between the substrate 1 and the peeling layer 4. In addition, the undercoat layer 2 and the back surface layer 5 are any one of the thermal transfer sheets of one embodiment.

A thermal transfer sheet 10 according to an embodiment is a thermal transfer sheet used to remove a specific area of a transfer layer of an intermediate transfer medium. Specifically, as shown in FIG. 2, the thermal transfer sheet 10 The peeling layer 4 overlaps the transfer layer 31 of the intermediate transfer medium 30, and energy is applied to the back side of the thermal transfer sheet 10 by a heating means 16 such as a thermal head, and the intermediate transfer corresponding to the area to which the energy is applied is transferred. A specific area of the transfer layer 31 of the print medium 30 is used to remove a thermal transfer sheet. Hereinafter, although the case where the transfer layer removed by the peeling layer 4 of the thermal transfer sheet 10 of one embodiment is a transfer layer of an intermediate transfer medium will be described as an example, the thermal transfer sheet 10 of one embodiment is described. The transfer layer removed by peeling the layer 4 may also be a transfer layer of a protective layer transfer sheet. The transfer layer of the intermediate transfer medium is composed of only a single layer formed by the receiving layer, or it is composed of a laminated layer composed of the receiving layer and other layers. The transfer layer of the intermediate transfer medium is peelable from the support. Ground setting. In addition, the transfer layer of the intermediate transfer medium exhibits a product of two or more layers. In layer construction, the receiving layer is located farthest from the support. In addition, the transfer layer of the protective layer transfer sheet may consist of only a single layer formed by the protective layer, or may consist of a laminated layer formed by laminating the protective layer and other layers. The transfer layer of the protective layer transfer sheet may be It is provided so as to be peeled from the support. Examples of the other layer include a peeling layer. In addition, the transfer layer of the intermediate transfer medium and the protective layer transfer sheet peeled from the support are configured to be transferable to the transfer target. It may be an object provided with a transfer layer other than these. In the following, the removal performance when a specific area of the transfer layer 31 of the intermediate transfer medium 30 is removed using the thermal transfer sheet 10 having the release layer 4 is referred to as "peelability". Here, the good releasability means that a specific region of the transfer layer can be accurately removed by the peeling layer 4, in other words, the target transfer layer 31 can be removed. In addition, the thermal transfer sheet referred to in the present specification is a general term for a medium suitable for heating means such as a thermal head. According to the present invention, it is used for removing a part of the transfer layer 31 of the intermediate transfer medium 30 by applying the heating means. A component in which the peeling layer 4 is provided on one side of the substrate is also included in the thermal transfer sheet.

(Base material)

The base material 1 constituting the thermal transfer sheet 10 according to one embodiment is not particularly limited, and a person conventionally known in the field of thermal transfer sheets can be appropriately selected and used. Examples include thin paper such as cellophane, capacitor paper, or paraffin paper, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, etc., polyphenylene sulfate, Polyether ketone or polyether fluorene and other heat-resistant polyesters, polypropylene, polycarbonate, cellulose acetate, polyethylene Stretched or unstretched films of plastics such as derivatives, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyimide, polyimide, polymethylpentene, or ionic polymers. A composite film obtained by laminating two or more of these materials may also be used.

The thickness of the substrate 1 is not particularly limited, but is preferably 2 μm or more and 10 μm or less. In order to improve the adhesion between the substrate 1 and the peeling layer 4 described later, the surface of the substrate 1 may be subjected to a subsequent treatment. That is, the substrate 1 subjected to the subsequent treatment may be used. Examples of the subsequent treatment include corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, roughening treatment, chemical treatment, plasma treatment, low-temperature plasma treatment, and graft treatment. Resin surface modification technology. In addition, two or more of these processes may be used in combination. In addition to using the substrate 1 subjected to the subsequent treatment, an undercoat layer 2 described below may be provided between the substrate 1 and the peeling layer 4 together with the substrate 1 subjected to the subsequent treatment.

(Stripping layer of the first form)

As shown in FIG. 2, the peeling layer 4 constituting the thermal transfer sheet 10 according to an embodiment is a layer that plays a role of removing a specific region (a region desired to be removed) of the transfer layer 31 of the intermediate transfer medium 30. Specifically, it is used to overlap the transfer layer 31 of the intermediate transfer medium 30 and the peeling layer 4 of the thermal transfer sheet 10, and the back side of the thermal transfer sheet 10 is heated by a heating means 16 such as a thermal head. Energy is applied to remove the transfer layer 31 at a position corresponding to the area where the energy is applied. The intermediate transfer medium 30 in the form shown in Figs. 2 and 3 has a structure in which a transfer layer 31 is provided on a support.

Here, the characteristic of the thermal transfer sheet 10 according to one embodiment is that the peeling layer 4 contains a vinyl chloride resin and an acrylic resin, and the mass of the vinyl chloride resin is more than 50% by mass relative to the total mass of the peeling layer 4. In addition, it is in a range of 95% by mass or less. Hereinafter, the peeling layer having this characteristic may be referred to as a peeling layer of the first aspect.

According to the thermal transfer sheet 10 which is one embodiment of the peeling layer of the first aspect, the specific area of the transfer layer 31 to be removed can be accurately removed by the peeling layer 4 of the first aspect.

Moreover, when the peeling layer 4 contains a vinyl chloride-type resin and an acrylic resin, when the mass of a vinyl chloride-type resin with respect to the total mass of the peeling layer 4 is 50 mass% or less, peelability cannot fully be satisfied. Specifically, the removal area of the transfer layer that is expected to be removed by the peeling layer and the transfer layer located near the boundary with the non-removed area cannot be removed correctly, and a part of the removal area of the transfer layer that should have been removed tends to remain in the middle On the transfer medium side, a specific area of the transfer layer 31 to be removed cannot be removed correctly. Alternatively, when the boundary between the removed area and the non-removed area is used as a starting point, the transfer layer of the non-removed area is dragged, and a part of the transfer layer of the non-removed area is removed, so that the transfer layer that should originally remain on the intermediate transfer medium side That is, the transfer layer of the non-removed area is removed together with the transfer layer corresponding to the removed area, and a specific area of the transfer layer 31 that is desired to be removed cannot be removed correctly.

When the peeling layer 4 contains a vinyl chloride resin and an acrylic resin, when the mass of the vinyl chloride resin relative to the total mass of the peeling layer 4 exceeds 95% by mass, the transfer layer of the intermediate transfer medium 30 The adhesion between 31 and stripping layer 4 is too strong, and it is easy to produce as shown in Figure 3, according to The peeling layer 4 that should have remained on the thermal transfer sheet 10 side becomes a problem on the intermediate transfer medium 30 side.

In addition, even when the peeling layer 4 contains a vinyl chloride resin in a range of more than 50% by mass and less than 95% by mass relative to the total mass of the peeling layer 4, when the acrylic resin is not contained, the base material 1 and The adhesiveness of the peeling layer 4 is reduced, and as shown in FIG. 3, the problem that the peeling layer 4 that should originally remain on the thermal transfer sheet 10 side becomes the side of the intermediate transfer medium 30 is easy to occur.

By containing a vinyl chloride resin and an acrylic resin, and the content of the vinyl chloride resin relative to the total mass of the peeling layer is in a range of more than 50% by mass and 95% by mass or less, improvement in peelability can be achieved. The mechanism is not clear at present, but it is at least clear from the results of the examples and comparative examples described below that the content of vinyl chloride resin and acrylic resin used in combination with vinyl chloride resin have an effect on the releasability.

The peeling layer 4 of the preferable 1st form contains a vinyl chloride resin in the range of 70 mass% or more and 90 mass% or less with respect to the total mass of the peeling layer 4, especially 80 mass% or more and 90 mass% or less. .

<Vinyl chloride resin>

The vinyl chloride resin referred to in this specification means a polymer obtained by homopolymerizing vinyl chloride, a copolymer of vinyl chloride and other monomers copolymerizable with vinyl chloride, and a mixture of the polymer and the copolymer. Examples of other monomers copolymerizable with vinyl chloride include, for example, vinylidene chloride, ethylene, propylene, and propylene Acrylonitrile, maleic acid, itaconic acid, acrylic acid, methacrylic acid, vinyl acetate, etc. These vinyl chloride-based resins can be produced by any one of conventionally known production methods such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a block polymerization method. Moreover, it may be a manufacturer by other methods.

Among these vinyl chloride-based resins, a vinyl chloride-vinyl acetate copolymer can be said to be a preferred vinyl chloride-based resin from the viewpoint of achieving further improvement in releasability.

In addition, as the vinyl chloride-based resin, a hardened vinyl chloride-based resin in which the above-mentioned vinyl chloride-based resin is hardened by a hardener may also be used. Examples of the curing agent include isocyanate-based curing agents.

The peeling layer 4 of the preferable 1st aspect contains the vinyl chloride-type resin whose number average molecular weight (Mn) is 10,000 or more and 30,000 or less. Moreover, the peeling layer 4 of the preferable 1st aspect contains the vinyl chloride-type resin whose glass transition temperature Tg is 60 degreeC or more and 80 degreeC or less. According to the stripping layer 4 of the preferred first form, the stripping property can be further improved. In addition, the number average molecular weight (Mn) referred to in the present specification means an average molecular weight in terms of polystyrene according to JIS-K7252-1 (2008) determined by GPC. The same applies to the weight average molecular weight (Mw) described later. In addition, the glass transition temperature (Tg) referred to in the present specification means a temperature obtained by a thermal change measurement (DSC method) based on DSC (differential scanning calorimetry) in accordance with JIS-K-7121 (2012).

<Acrylic resin>

The acrylic resin referred to in this specification means acrylic acid or methacrylic acid. Polymers of acid monomers, or derivatives thereof, polymers of acrylate or methacrylate monomers, or derivatives thereof, copolymers of acrylic or methacrylic monomers with other monomers, or Derivatives, copolymers of acrylate or methacrylate monomers and other monomers, or their derivatives, copolymers of acrylic monomers and acrylate monomers, copolymerization of acrylic monomers and methacrylate monomers Polymers, copolymers of methacrylic monomers and acrylate monomers, copolymers of methacrylic monomers and methacrylate monomers.

Examples of the acrylate and methacrylate monomers include cyclohexyl acrylate, cyclohexyl methacrylate, pentyl acrylate, pentyl methacrylate, phenoxyethyl acrylate, and phenoxyethyl methacrylate. Ester, isobornyl acrylate, isobornyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, Propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, third butyl acrylate, third butyl methacrylate, isodecyl acrylate , Isodecyl methacrylate, lauryl acrylate, lauryl methacrylate, lauryl tridecyl acrylate, lauryl tridecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, Cetyl stearyl acrylate, cetyl stearyl methacrylate, stearyl acrylate, stearyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, acrylic acid Octyl ester, octyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, methacrylic acid , Acrylic acid, 2-hydroxyethyl acrylate, methacrylic acid 2-hydroxyethyl acid, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, methyl Diethylaminoethyl acrylate, tertiary butylamino acrylate, tertiary butylamino methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, methacrylic acid Tetrahydrofurfuryl ester, ethylene diacrylate, ethylene dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol diacrylate Methacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, decaethylene glycol diacrylate, decaethylene glycol dimethacrylate, pentaethylene glycol diacrylate, Fifteen ethylene glycol dimethacrylate, pentacontahectaethylene glycol diacrylate, one hundred and fifty ethylene glycol dimethacrylate, butyl diacrylate, butyl dimethacrylate Diester, allyl acrylate, allyl methacrylate , Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, tripropylene glycol diacrylate , Tripropylene glycol dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, neopentyl glycol pentaacrylate, neopentyl glycol pentamethyl Acrylate, phosphazene hexaacrylate, phosphazene hexamethacrylate and the like.

Examples of other monomers include aromatic hydrocarbons, compounds containing propylene groups, compounds containing fluorenyl groups, vinyl chloride, and the like, styrene, benzylstyrene, phenoxyethyl methacrylate, acrylamide, Methyl Acrylamide and so on.

Examples of the acrylic resin include, for example, one or two or more alkyl acrylates, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2 (meth) acrylic acid. -One or two or more (meth) acrylates having a hydroxyl group in a molecule such as hydroxy-3-phenoxypropyl, and one or two or more other polymerizable monomers such as styrene as necessary Acrylic polyol resin and the like obtained by copolymerization.

The peeling layer 4 of the preferable 1st aspect contains the acrylic resin whose weight average molecular weight (Mw) is 20,000 or more and 50,000 or less. In addition, the preferred peeling layer 4 of the first aspect contains an acrylic resin having a glass transition temperature (Tg) of 80 ° C to 120 ° C. According to the stripping layer 4 of the preferred first form, the stripping property can be further improved.

In addition, as the acrylic resin, a hardened acrylic resin that hardens the acrylic resin with a curing agent may be used. Examples of the curing agent include isocyanate-based curing agents.

The content of the acrylic resin is not particularly limited, but it is preferably in a range of 10% by mass or more and 30% by mass or less with respect to the total mass of the peeling layer 4 in the first aspect.

The peeling layer 4 of the first aspect may contain other components together with the vinyl chloride resin and the acrylic resin. Examples of other components include celluloses such as polyester resins, ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, and nitro cellulose. Resin, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, etc. Resins, acrylic resins such as polymethyl methacrylate, polyethyl acrylate, polyacrylamide, acrylonitrile-styrene copolymers, polyamidamine resin, polyvinyl toluene resin, coumarone indene resin, poly Monomers or mixtures of natural or synthetic resins such as urethane resins, polysiloxane-modified or fluorine-modified urethanes.

The method for forming the peeling layer 4 of the first aspect is not particularly limited, and it can be prepared by adding additives such as vinyl chloride resin, acrylic resin, and any resin as needed, and inorganic or organic fillers. The coating liquid for a layer is formed by coating the coating liquid on the base material 1 or any layer provided on the base material 1 and drying it. The coating method of the coating liquid for a peeling layer is not specifically limited, A conventionally well-known coating method can be selected suitably and used. Examples of the coating method include a gravure printing method, a screen printing method, and a reverse roll coating method using a gravure. Moreover, other coating methods may be used. The same applies to various coating liquids described later.

The thickness of the peeling layer 4 of the first aspect is not particularly limited, but it is preferably in a range of 0.1 μm to 5 μm. The same applies to the peeling layer 4 of the second aspect described later.

(Stripping layer of the second form)

Instead of the peeling layer 4 of the first form described above, the second form using a polyester resin containing a number average molecular weight (Mn) of 17,000 or less and a glass transition temperature (Tg) of 50 ° C or higher and 120 ° C or lower may be used. The stripping layer 4. According to the thermal transfer sheet 10 having the peeling layer 4 of the second aspect, a specific region of the transfer layer 31 to be removed can be accurately removed. Especially, even When the thickness of the transfer layer 31 is increased, a specific region of the transfer layer 31 to be removed can also be accurately removed. In addition, in this specification, when it is only called a peeling layer, it means both the peeling layer of a 1st form and a 2nd form.

The feature of the peeling layer 4 of the second aspect is that the polyester resin contained in the peeling layer 4 of the second aspect is a polyester resin that satisfies the following conditions 1 and 2.

Condition 1: The number average molecular weight (Mn) of the polyester-based resin is 17,000 or less.

Condition 2: The glass transition temperature (Tg) of the polyester resin is within a range of 50 ° C to 120 ° C.

Hereinafter, the polyester resin which satisfies the conditions 1 and 2 may be referred to as a "specific polyester resin".

In addition, instead of the "specific polyester resin", the peeling layer contains a polyester resin that does not satisfy any one or both of conditions 1 and 2, or a resin different from the "specific polyester resin". Time, it cannot fully satisfy the stripping property. Specifically, the transfer layer located near the boundary between the removed area and the non-removed area of the transfer layer that is expected to be removed by the peeling layer cannot be removed correctly, and a part of the removed area of the transfer layer that should have been removed tends to remain in the intermediate transfer. On the printing medium side, specific areas of the transfer layer 31 that are desired to be removed cannot be removed correctly. Or, when the boundary between the removed area and the non-removed area is used as a starting point, the transfer layer of the non-removed area will be dragged to remove a part of the transfer layer of the non-removed area, so that the transfer layer that should originally remain on the intermediate transfer medium side That is, the transfer layer in the non-removed area will be removed together with the transfer layer corresponding to the removed area, and the specificity of the transfer layer 31 that is desired to be removed cannot be removed correctly. region.

The mechanism for improving the releasability by using the second layer of the "specific polyester-based resin" as the peeling layer 4 is not yet clear, but at least the results of the examples and comparative examples described later, The number average molecular weight (Mn) and the glass transition temperature (Tg) of the polyester-based resin exert influence on the releasability.

The polyester resin referred to in this specification means an ester group-containing polymer obtained by polycondensation of a polycarboxylic acid and a polyhydric alcohol. Examples of the polycarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, decanedicarboxylic acid, azelaic acid, and deca Dioxanedicarboxylic acid, cyclohexanedicarboxylic acid, etc. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, decanediol, and 2-ethylbutane. 1-propanediol, bisphenol A, etc. Furthermore, the polyester resin can be copolymerized with more than three kinds of polycarboxylic acids and polyhydric alcohols, and can also be a copolymer with monomers or polymers such as diethylene glycol, triethylene glycol, and polyethylene glycol. . The polyester-based resin referred to in the present specification also includes modified products of the polyester-based resin. Examples of the modified product of the polyester-based resin include a polyester urethane resin and the like.

The peeling layer 4 of the second aspect may contain other components together with the "specific polyester resin". Examples of the other component include, for example, a polyester resin that does not satisfy any one or both of the conditions 1 and 2, or other components described in the peeling layer 4 of the first aspect.

In addition, the peeling layer 4 of the second aspect may contain a number average molecular weight (Mn) or a glass transition temperature (Tg) that satisfies the conditions 1 and 2 described above. Same as two or more "specific polyester resins".

The content of the "specific polyester-based resin" is not limited. Regardless of the content, as long as the "specific polyester-based resin" is contained in the peeling layer 4, the peelability can be improved. As an example, the content of the "specific polyester resin" is 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more, and particularly good with respect to the total mass of the peeling layer 4 in the second form. It is 20% by mass or more. The upper limit value is not limited, but may be 100% by mass.

The lower limit of the number-average molecular weight (Mn) of the "specific polyester-based resin" is not particularly limited, but is preferably 2500 or more, and more preferably 3500 or more.

A preferred second embodiment of the peeling layer 4 contains a polyester resin having a number average molecular weight (Mn) of less than 9,000, more preferably 8,000 or less and satisfying the above Condition 2 as a "specific polyester resin". In addition, the preferable peeling layer 4 of the second aspect contains a polyester resin that satisfies the above Condition 1 and has a glass transition temperature (Tg) of 50 ° C or higher and 100 ° C or lower as a "specific polyester resin". The second preferred form of the peeling layer 4 contains a polyester resin having a number average molecular weight (Mn) of less than 9,000, more preferably 8,000 or less, and a glass transition temperature (Tg) of 50 ° C or higher and 100 ° C or lower as a "specific polyester series" Resin. " According to the stripping layer 4 of these preferred second forms, the stripping property can be further improved.

The method for forming the peeling layer 4 in the second form is not particularly limited, and it can be prepared by adding a "specific polyester-based resin" and an optional resin as required, and an additive material such as an inorganic or organic filler. use The coating liquid is formed by coating the coating liquid on the base material 1 or any layer provided on the base material 1 and drying it.

(Undercoat)

As shown in FIG. 1, an undercoat layer 2 may also be provided between the substrate 1 and the peeling layer 4. Since the undercoat layer 2 is provided between the base material 1 and the peeling layer 4, when a specific area of the transfer layer 31 is removed by the peeling layer 4, it should originally remain on the thermal transfer sheet 10 together with the removed transfer layer. The peeling layer 4 on the side moves to the intermediate transfer medium side, and the reverse transfer of the so-called peeling layer can be sufficiently suppressed. In particular, when the energy applied to the thermal transfer sheet is increased when the transfer layer of the intermediate transfer medium is removed by the peeling layer, the reverse transfer of the peeling layer tends to occur. Therefore, in this case, an undercoat layer is preferably provided. 2.

Examples of the material constituting the undercoat layer 2 include polyester resin, polyacrylate resin, polyvinyl acetate resin, polyurethane resin, styrene acrylate resin, and polypropylene resin. , Vinyl resins, polyether resins, polystyrene resins, polyethylene resins, polypropylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, and polyvinylpyrrolidone resins , Polyvinyl acetal resin such as polyethylene acetal or polyvinyl butyral, etc., inorganic particles, etc.

The thickness of the undercoat layer 2 is preferably 0.03 μm or more, and more preferably 0.06 μm or more. The upper limit value is not particularly limited, but is about 1 μm.

The formation method of the undercoat layer 2 is not particularly limited, and can be modulated The coating liquid for an undercoat layer in which the materials and the like exemplified above are dissolved or dispersed in an appropriate solvent, and the coating liquid is coated on the substrate 1 and dried to form it.

(Back layer)

As shown in FIG. 1, a back layer 5 may be provided on the other surface of the substrate 1. In addition, the back surface layer 5 has an arbitrary configuration in the thermal transfer sheet 10 according to an embodiment.

The material of the back layer 5 is not limited, and examples thereof include ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, nitro cellulose, and the like. Cellulose resins, vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl pyrrolidone, polymethyl methacrylate, polyethyl acrylate, poly Acrylic resins such as acrylamide, acrylonitrile-styrene copolymers, polyamide resins, polyvinyl toluene resins, coumarone indene resins, polyester resins, polyurethane resins, polysiloxanes Monomers or mixtures of natural or synthetic resins such as modified or fluorine-modified urethanes.

The back layer 5 may contain a solid or liquid lubricant. Examples of lubricants include various waxes such as polyethylene waxes, paraffinic waxes, higher aliphatic alcohols, organic polysiloxanes, anionic surfactants, cationic surfactants, amphoteric surfactants, and anionic interfaces. Active agents, fluorine-based surfactants, organic carboxylic acids and their derivatives, metal soaps, fluorine-based resins, silicone resins, talc, fine particles of inorganic compounds such as silica, etc. The mass of the lubricant relative to the total mass of the back layer 5 is 5 The range of mass% to 50 mass% is preferably a range of 10 mass% to 30 mass%.

The method for forming the back surface layer 5 is not particularly limited, and a coating liquid for the back surface layer that dissolves or disperses a resin and a lubricant added as necessary in an appropriate solvent can be prepared, and the coating liquid is applied to the substrate 1 Form and dry. The thickness of the back layer 5 is preferably in a range of 1 μm to 10 μm.

In addition, as shown in FIG. 4, the thermal transfer sheet 10 according to an embodiment may be provided with yellow (Y) and magenta (M) sequentially in the same order on the same surface of the substrate 1 on which the peeling layer 4 is provided. ), Each of the cyan (C) dye layers 7 (7 (Y), 7 (M), 7 (C)), and the black (Bk) melt layer 8 is constituted. The dye layer 7 and the fused layer 8 are arbitrarily configured in the thermal transfer sheet 10 according to an embodiment. Moreover, instead of these arbitrary layers, a transferable protective layer (not shown) may be provided in sequence with these layers.

(Dye layer)

The dye layer 7 contains a sublimable dye, a binder resin, and any components added as needed. Sublimation dyes, binder resins, and the like can be used conventionally, and are not particularly limited. The dye layer can be prepared by dissolving or dispersing a sublimable dye, a binder resin, and any components added as necessary in a suitable solvent, and coating the coating liquid on the substrate 1 and drying the coating liquid. And formed. The thickness of the dye layer is usually in a range of 0.2 μm to 3 μm.

In addition, between the base material 1 and the dye layer 7, it is also possible to provide The conventional dye base coat (not shown).

(Melted Layer)

The molten layer 8 can be formed using a conventionally known hot-melt ink, and various additives can be added as necessary. These materials can be used by those who are known in the past without particular limitation. The melted layer 8 is formed by applying a hot-melt ink to the substrate 1 by using a method such as a gravure printing method or a hot-melt coating method and drying it. The thickness of the molten layer is determined by the relationship between the required concentration and the thermal sensitivity, and is usually in the range of about 0.2 μm to 10 μm.

<Stripped area>

Next, referring to FIG. 5, an example of a removal area of the transfer layer removed by the peeling layer 4 of the thermal transfer sheet 10 according to an embodiment will be described. FIG. 5 is a schematic plan view of an intermediate transfer medium 30 used in combination with the thermal transfer sheet 10 according to an embodiment. The blank area (symbols A and B on the way) is a peeling of the thermal transfer sheet 10 according to an embodiment. Remove the area removed by layer 4.

The area where the transfer layer 31 is removed is not particularly limited. For example, as shown by the symbol A in FIG. In other words, the area that has not been transferred to the object to be transferred can be removed by removing the frame with the peeling layer 4. For example, as shown by the symbol B in FIG. 5, in the transfer target body to which the transfer layer 31 is finally transferred, the area where the accessory such as an IC chip or a signature column is mounted, that is, where the transfer is transferred In the transferred body of the layer 31, a defective area occurs when the transfer layer 31 remains.

<Heating method>

The heating means for removing a specific area of the transfer layer 31 by the peeling layer 4 is not particularly limited, and for example, a thermal head, a heating means using a light source or a laser light source, and the like can be used. In addition, the heating means for transferring the transfer layer 31 removed from the specific region by the peeling layer 4 to the object to be transferred is not limited, and examples thereof include a heating roller method, a hot stamping method, and a thermal head method.

The intermediate transfer medium used in combination with the thermal transfer sheet 10 according to an embodiment is not limited to the illustrated form, and any of the conventionally known intermediate transfer media may be applied. In addition, instead of an intermediate transfer medium, a protective layer transfer sheet in which a transfer layer including a protective layer is provided on a support may be used.

<< Combination of transfer foil and thermal transfer sheet >>

Next, a combination of a transfer foil and a thermal transfer sheet according to the embodiment of the present disclosure (hereinafter referred to as a combination of one embodiment) will be described. The combination of one embodiment is characterized by a combination of a transfer foil provided with a transfer layer peelable from the support on a support, and a thermal transfer sheet provided with a peeling layer on a substrate to transfer The transfer foil and thermal transfer sheet are overlapped with the layer and the peeling layer facing each other. The transfer speed of the thermal transfer sheet is 42.3mm / sec, and the energy applied to the thermal transfer sheet is 0.143mJ / dot. The adhesion between the transfer layer and the peeling layer measured when a specific area of the transfer layer was removed by the peeling layer was 0.03 N / cm or more. In the following, the transfer foil and the thermal transfer sheet are stacked so that the transfer layer and the peeling layer face each other. The transfer speed of the thermal transfer sheet is 42.3 mm / sec, and the energy applied to the thermal transfer sheet is 0.143 mJ / dot condition is called "special "Specific measurement conditions", and using the "specific measurement conditions", the adhesion between the transfer layer and the peeling layer measured when a specific area of the transfer layer is removed by the peeling layer is sometimes referred to as the transfer layer and the peeling layer. The close adhesion.

In addition, the above-mentioned "specific measurement conditions" are such that a specific region of the transfer layer is removed by the peeling layer so that the peeling angle of the transfer layer peeled from the support is 50 °.

According to the combination of the embodiment in which the adhesion between the transfer layer and the peeling layer measured according to "specific measurement conditions" is 0.03 N / cm or more, a specific region of the transfer layer can be accurately removed by the peeling layer.

The combination of the preferable form is that the adhesion between the transfer layer and the peeling layer measured under "specific measurement conditions" is 0.05 N / cm or more, and further 0.18 N / cm or more, and especially 0.2 N / cm or more. The combination of the best form is a condition in which the transfer speed of the thermal transfer sheet is 42.3 mm / sec, and the energy applied to the thermal transfer sheet is in the range of 0.1 mJ / dot to 0.2 mJ / dot. The adhesion between the transfer layer and the peeling layer measured when a specific area of the transfer layer is removed is 0.03 N / cm or more, and especially becomes the adhesion of the combination of the above-mentioned preferred forms. The upper limit of the adhesion force between the transfer layer and the peeling layer measured under "specific measurement conditions" is not particularly limited, but as an example of the adhesion force range, a range from 0.03N / cm to 1N / cm or less, or 0.03N / The range is from cm to 0.7 N / cm.

In the combination of one embodiment, the adhesion between the transfer layer and the peeling layer is such that the transfer layer of the transfer foil and the peeling layer of the thermal transfer sheet overlap, and as shown in FIG. 6, a printer 200 is used. On the condition that the transfer speed of the thermal transfer sheet is 42.3 mm / sec and the applied energy is 0.143 mJ / dot, Peeling layer of transfer sheet The value of tensile strength measured by measuring means 204 when removing the transfer layer of transfer foil. The printer 200 includes thermal transfer sheet supply means 201, heating means 202, and thermal transfer sheet. Winding means 203, measuring means 204 located between heating means 202 and thermal transfer sheet winding means 203 for measuring the tensile strength of the thermal transfer sheet conveyed along the conveying path, and measuring means 204 located between heating means 202 and measuring means 204 Stripping means 205. The value of the tensile strength can be regarded as the adhesion between the transfer layer and the peeling layer.

The applied energy (mJ / dot) referred to in this specification is the applied energy calculated by the following formula (1), and the applied power [W] in the formula (1) can be calculated by the following formula (2).

Applied energy (mJ / dot) = W × L.S × P.D × Hue value ... (Formula (1))

(In the formula (1), [W] means applied power, [L.S] means 1-line period (msec / line), and [P.D] means pulse duty cycle.)

Applied power (W / dot) = V ² /R...(Formula (2))

([V] in formula (2) means applied voltage, [R] means resistance value of heating means)

The transport speed (mm / sec.) Of the thermal transfer sheet referred to in this specification is a transport speed calculated from the following formula (3).

Transport speed (mm / sec.) = (25.4 × 1000) / (printing density in the sub-scanning direction (dot / inch)) × line period (msec / line) ... (formula (3))

(25.4 in formula (3) is a value used to convert inches to mm).

The method for making the adhesion between the transfer layer and the peeling layer 0.03 N / cm or more is not particularly limited. As a countermeasure for the thermal transfer sheet side, For example, the method of adjusting the composition of the peeling layer, the method of adjusting the thickness of the peeling layer or the substrate, and the like. In addition, as a countermeasure for the transfer foil side, a method of adjusting the composition of the transfer layer or the thickness of the transfer layer can be exemplified. In addition, the adhesion between the transfer layer and the peeling layer can be set to 0.03 N / cm or more by countermeasures of both the thermal transfer sheet and the transfer foil.

That is, if the transfer foil and thermal transfer sheet used in the combination of one embodiment satisfy the condition that the adhesion between the transfer layer and the peeling layer measured by "specific measurement conditions" is 0.03 N / cm or more, The conditions are not limited.

The use of the transfer foil used in the combination of one embodiment is not particularly limited, and examples thereof include an intermediate transfer medium that can transfer a transfer layer containing a receiving layer on a transferee, or a transfer medium containing a protective layer. The transfer layer is a protective layer transfer sheet or the like, which is transferred onto the object to be transferred. Moreover, if it is a medium which can transfer a transfer layer on a to-be-transferred body, you may use other than this.

[Example]

The following examples further illustrate the present invention. Unless otherwise specified, parts are based on mass. Tg means glass transition temperature, Mn means index average molecular weight, and Mw means weight average molecular weight.

(Example A-1)

A 4.5 μm-thick polyethylene terephthalate film is used as a substrate, and the easily-adhesive surface of one side of the substrate is used as the substrate. The coating liquid 1 for a peeling layer having the following composition was applied so as to have a thickness of 1 μm during drying, and dried to form a peeling layer. In addition, on the other side of the substrate, a coating liquid for a back surface layer having the following composition was applied so as to have a thickness of 0.8 μm when dried, and dried to form a back layer, thereby obtaining a thermal transfer sheet of Example A-1. .

<Coating liquid for peeling layer 1>

<Coating liquid for back layer>

(Example A-2)

Except that the coating liquid 1 for a peeling layer was changed to the coating liquid 2 for a peeling layer having the following composition, the thermal transfer sheet of Example A-2 was obtained in the same manner as in Example A-1.

<Coating liquid for peeling layer 2>

(Example A-3)

A thermal transfer sheet of Example A-3 was obtained in the same manner as in Example A-1 except that the coating liquid for peeling layer 1 was changed to the coating liquid 3 for peeling layer having the following composition.

<Coating liquid 3 for peeling layer>

(Example A-4)

A thermal transfer sheet of Example A-4 was obtained in the same manner as in Example A-1 except that the coating liquid for peeling layer 1 was changed to the coating liquid 4 for peeling layer having the following composition.

<Coating liquid 4 for peeling layer>

(Example A-5)

Except that the coating liquid 1 for a peeling layer was changed to the coating liquid 5 for a peeling layer having the following composition, the thermal transfer sheet of Example A-5 was obtained in the same manner as in Example A-1.

<Coating liquid 5 for peeling layer>

‧80 parts of methyl ethyl ketone

(Comparative Example A-1)

Except that the coating liquid 1 for a peeling layer was changed to the coating liquid A for a peeling layer having the following composition, the thermal transfer sheet of Comparative Example A-1 was obtained in the same manner as in Example A-1.

<Coating liquid A for peeling layer>

(Comparative example A-2)

A thermal transfer sheet of Comparative Example A-2 was obtained in the same manner as in Example A-1 except that the coating liquid for peeling layer 1 was changed to the coating liquid B for peeling layer having the following composition.

<Coating liquid B for peeling layer>

(Comparative Example A-3)

Except having changed the coating liquid 1 for peeling layers into the coating liquid C for peeling layers of the following composition, it carried out similarly to Example A-1, and obtained the thermal transfer sheet of the comparative example A-3.

<Coating liquid C for peeling layer>

(Comparative Example A-4)

A thermal transfer sheet of Comparative Example A-4 was obtained in the same manner as in Example A-1 except that the coating liquid for peeling layer 1 was changed to the coating liquid D for peeling layer having the following composition.

<Coating liquid D for peeling layer>

(Comparative Example A-5)

In addition, the coating liquid 1 for a peeling layer was changed to a coating for a peeling layer having the following composition Except for the cloth liquid E, the heat transfer sheet of Comparative Example A-5 was obtained in the same manner as in Example A-1.

<Coating liquid E for peeling layer>

(Production of intermediate transfer media (1))

A 12 μm-thick polyethylene terephthalate film (LUMIRROR (registered trademark) Toray Co., Ltd.) was used as a support, and the following composition was applied to the support so that the thickness was 1.6 μm when dried. The coating liquid for a release layer is dried to form a release layer. Next, on the release layer, a coating liquid for a protective layer having the following composition was applied so as to have a thickness of 4.7 μm when dried, and dried to form a protective layer. Next, on the protective layer, a coating liquid for a receiving layer having the following composition was applied so as to have a thickness of 2 μm when dried, and dried to form a receiving layer, thereby obtaining an intermediate transfer medium (1). The coating liquid for a release layer, the coating liquid for a protective layer, and the coating liquid for a receiving layer were all applied using a gravure printing method.

<Coating liquid for release layer>

‧20 parts of acrylic resin (DIANAL (registered trademark) BR83 Mitsubishi Electric Co., Ltd.)

<Coating liquid for protective layer>

<Coating liquid for receiving layer>

<Exfoliation test>

On the receiving layer of the intermediate transfer medium (1) prepared as described above, a thermal transfer image of a photo tone of sublimation transfer is formed. Next, the receiving layer of the intermediate transfer medium (1) forming the thermal transfer image was brought into contact with the peeling layer of the thermal transfer sheet of each of the examples and comparative examples prepared as described above, and the following printer was used. , Heating the back side of the thermal transfer sheet, and removing the special characteristics of the transfer layer of the laminated body of the release layer, the protective layer and the receiving layer from the intermediate transfer medium (1) Fixed area. The state of removal of the transfer layer at this time and the state of peeling when the peeling layer was peeled from the intermediate transfer medium (1) were visually confirmed, and the peelability and the peelability of the peeling layer were evaluated based on the following evaluation criteria. The evaluation results are shown in Table 1.

(Printer)

Thermal head: KEE-57-12GAN2-STA (KYOCERA (shares))

Average resistance value of heating element: 3303 (Ω)

Printing density in main scanning direction: 300 (dpi)

Printing density in sub-scanning direction: 300 (dpi)

Line period: 2 (msec / line)

Printing start temperature: 35 (℃)

Pulse duty cycle: 85 (%)

Applied voltage: 21 (V)

(Exfoliative evaluation (1)) "Evaluation criteria"

A ... Correctly remove the transfer layer corresponding to the "specific area".

B ... A part of the transfer layer corresponding to the "specific area" is left slightly, or the transfer layer is removed slightly beyond the "specific area", but it is not a problem in use.

C ... A part of the transfer layer corresponding to the "specific area" remains, or the transfer layer is removed in a way beyond the "specific area", but to the extent that it is not a problem in use.

NG (1) ... does not properly remove the transfer layer corresponding to the "specific area" As bad.

NG (2) ... The transfer layer corresponding to the "specific area" is not removed at all and is defective.

(Evaluation of peelability of peeling layer) "Evaluation criteria"

A ... The peeling layer is not transferred to the intermediate transfer medium.

NG ... A part of the peeling layer was transferred to the intermediate transfer medium and was defective.

(Example B-1)

A 4.5 μm-thick polyethylene terephthalate film is used as a substrate, and the easily-adhesive surface of one side of the substrate is used as the substrate. The coating liquid 11 for a peeling layer having the following composition was applied so as to have a thickness of 1 μm during drying, and dried to form a peeling layer. In addition, a coating liquid for a back surface layer having the above composition was applied on the other surface of the base material to have a thickness of 0.8 μm when dried, and dried to form a back layer, thereby obtaining a thermal transfer sheet of Example B-1.

<Coating liquid for peeling layer 11>

(Example B-2)

A thermal transfer sheet of Example B-2 was obtained in the same manner as in Example B-1 except that the coating liquid for peeling layer 11 was changed to the coating liquid for peeling layer 12 having the following composition.

<Coating liquid for peeling layer 12>

(Example B-3)

A thermal transfer sheet of Example B-3 was obtained in the same manner as in Example B-1 except that the coating liquid for peeling layer 11 was changed to the coating liquid 13 for peeling layer having the following composition.

<Coating liquid for peeling layer 13>

(Example B-4)

A thermal transfer sheet of Example B-4 was obtained in the same manner as in Example B-1 except that the coating liquid for peeling layer 11 was changed to the coating liquid 14 for peeling layer having the following composition.

<Coating liquid 14 for peeling layer>

(Example B-5)

A thermal transfer sheet of Example B-5 was obtained in the same manner as in Example B-1 except that the coating liquid for peeling layer 11 was changed to the coating liquid 15 for peeling layer having the following composition.

<Coating liquid for peeling layer 15>

‧20 parts of polyester resin (Tg: 67 ° C, Mn: 17000) (HYRON (registered trademark) 200 Toyobo Co., Ltd.)

‧80 parts of methyl ethyl ketone

(Example B-6)

A thermal transfer sheet of Example B-6 was obtained in the same manner as in Example B-1 except that the coating liquid for peeling layer 11 was changed to the coating liquid 16 for peeling layer having the following composition.

<Coating liquid for peeling layer 16>

(Example B-7)

Except that the coating liquid 11 for a peeling layer was changed to the coating liquid 17 for a peeling layer having the following composition, the thermal transfer sheet of Example B-7 was obtained in the same manner as in Example B-1.

<Coating liquid for peeling layer 17>

(Example B-8)

For removing the coating liquid 11 for a peeling layer, for a peeling layer having the following composition Except for the coating liquid 18, the same procedure as in Example B-1 was performed to obtain a thermal transfer sheet of Example B-8.

<Coating liquid for peeling layer 18>

(Example B-9)

Except that the coating liquid 11 for a peeling layer was changed to the coating liquid 19 for a peeling layer having the following composition, the thermal transfer sheet of Example B-9 was obtained in the same manner as in Example B-1.

<Coating liquid for peeling layer 19>

‧80 parts of methyl ethyl ketone

(Example B-10)

Except that the coating liquid 11 for a peeling layer was changed to the coating liquid 20 for a peeling layer having the following composition, the thermal transfer sheet of Example B-10 was obtained in the same manner as in Example B-1.

<Coating liquid for peeling layer 20>

(Comparative Example B-1)

Except that the coating liquid 11 for a peeling layer was changed to the coating liquid F for a peeling layer having the following composition, it was the same as in Example B-1, and a thermal transfer sheet of Comparative Example B-1 was obtained.

<Coating liquid F for peeling layer>

(Comparative Example B-2)

A thermal transfer sheet of Comparative Example B-2 was obtained in the same manner as in Example B-1 except that the coating liquid for peeling layer 11 was changed to the coating liquid G for peeling layer having the following composition.

<Coating liquid G for peeling layer>

(Comparative Example B-3)

A thermal transfer sheet of Comparative Example B-3 was obtained in the same manner as in Example B-1 except that the coating liquid 11 for a peeling layer was changed to the coating liquid H for a peeling layer having the following composition.

<Coating liquid H for peeling layer>

(Comparative Example B-4)

Except that the coating liquid 11 for a peeling layer was changed to the coating liquid I for a peeling layer having the following composition, the heat transfer sheet of Comparative Example B-4 was obtained in the same manner as in Example B-1.

<Coating liquid I for peeling layer>

(Comparative Example B-5)

A thermal transfer sheet of Comparative Example B-5 was obtained in the same manner as in Example B-1 except that the coating liquid 11 for a peeling layer was changed to a coating liquid J for a peeling layer having the following composition.

<Coating liquid for peeling layer J>

(Comparative Example B-6)

Except that the coating liquid 11 for a peeling layer was changed to the coating liquid K for a peeling layer having the following composition, the heat transfer sheet of Comparative Example B-6 was obtained in the same manner as in Example B-1.

<Coating liquid K for peeling layer>

‧20 parts of polyester resin (Tg: -70 ° C, Mn: 30,000) (HYRON (registered trademark) GM913 UNITIKA (share))

‧80 parts of methyl ethyl ketone

(Production of Intermediate Transfer Media (2))

In addition to applying a coating liquid for a release layer having the above composition so as to have a thickness of 0.7 μm when drying and drying to form a release layer, applying a coating liquid for a protective layer having the above composition so as to be 1.5 μm in thickness when drying, and drying A protective layer was formed, and the coating liquid for a receiving layer having the above composition was applied so as to have a thickness of 0.7 μm when dried and dried to form a receiving layer. Print media (2). Moreover, compared with the intermediate transfer medium (1) and the intermediate transfer medium (2), the entire transfer layer of the laminated body of the release layer, the protective layer, and the receiving layer is thick, and the intermediate transfer is liable to have a low peelability. media.

<Peeling test (2)>

On the receiving layer of the intermediate transfer medium (1) prepared as described above, a thermal transfer image of a photo tone of sublimation transfer is formed. Next, the receiving layer of the intermediate transfer medium (1) forming the thermal transfer image was brought into contact with the peeling layer of the thermal transfer sheet of each of the examples and comparative examples prepared as described above, and the following printer was used. The voltages shown in Table 2 were applied to the back side of the thermal transfer sheet, respectively, and specific areas of the transfer layer of the laminate of the release layer and the protective layer and the receiving layer were removed from the intermediate transfer medium (1). The removal condition of the transfer layer at this time was visually confirmed, and the releasability was evaluated based on the following evaluation criteria. The same evaluation was performed on the intermediate transfer medium (2). The evaluation results are shown in Table 2. In addition, in the applied voltage 21 (V), both the intermediate transfer media (1) and (2) obtained good results. Evaluators of good peelability are used as examples.

(Printer)

Thermal head: KEE-57-12GAN2-STA (KYOCERA (shares))

Average resistance value of heating element: 3303 (Ω)

Printing density in main scanning direction: 300 (dpi)

Printing density in sub-scanning direction: 300 (dpi)

Line period: 2 (msec / line)

Printing start temperature: 35 (℃)

Pulse duty cycle: 85 (%)

Applied voltage: 18 (V) ~ 27 (V)

"Evaluation criteria"

A ... Correctly remove the transfer layer corresponding to the "specific area".

B ... A part of the transfer layer corresponding to the "specific area" is left slightly, or the transfer layer is removed slightly beyond the "specific area", but it is not a problem in use.

C ... A part of the transfer layer corresponding to the "specific area" remains, or the transfer layer is removed in a way beyond the "specific area", but to the extent that it is not a problem in use.

NG (1) ... defective because the transfer layer corresponding to "specific area" was not removed correctly.

NG (2) ... The transfer layer corresponding to the "specific area" is not removed at all and is defective.

(Production of thermal transfer sheet 1)

A 4.5 μm-thick polyethylene terephthalate film was used as a substrate, and the following composition was applied on the easily-adhesive surface of one side of the substrate to a thickness of 1 μm when dried. The coating liquid for peeling layer 31 is dried to form a peeling layer. In addition, on the other surface of the substrate, a coating liquid for a back surface layer having the above composition was applied so as to have a thickness of 0.8 μm when dried, and dried to form a back surface layer, thereby obtaining a thermal transfer sheet 1.

<Coating liquid for peeling layer 31>

(Production of thermal transfer sheet 2)

A thermal transfer sheet 2 was obtained in the same manner as in the method for producing the thermal transfer sheet 1 except that the coating solution for the peeling layer 31 was changed to the coating solution for the peeling layer 32 having the following composition.

<Coating liquid for peeling layer 32>

(Production of thermal transfer sheet 3)

The thermal transfer sheet 3 was obtained in the same manner as in the method for producing the thermal transfer sheet 1 except that the coating solution for the peeling layer 31 was changed to the coating solution 33 for the peeling layer having the following composition.

<Coating liquid for peeling layer 33>

(Production of thermal transfer sheet 4)

The thermal transfer sheet 4 was obtained in the same manner as in the method for producing the thermal transfer sheet 1 except that the coating solution for the peeling layer 31 was changed to the coating solution 34 for the peeling layer having the following composition.

<Coating liquid for peeling layer 34>

‧ Polyester resin (Tg = 67 ° C, Mn: 17000) 20 parts (HYRON (registered trademark) 200 Toyobo (stock))

‧80 parts of methyl ethyl ketone

(Production of thermal transfer sheet 5)

A thermal transfer sheet 5 was obtained in the same manner as the method for producing the thermal transfer sheet 1 except that the coating solution for the peeling layer 31 was changed to the coating solution 35 for the peeling layer having the following composition.

<Coating liquid for peeling layer 35>

(Production of thermal transfer sheet 6)

A thermal transfer sheet 6 was obtained in the same manner as in the method for producing the thermal transfer sheet 1 except that the coating solution for the peeling layer 31 was changed to the coating solution 36 for the peeling layer having the following composition.

<Coating liquid for peeling layer 36>

(Production of thermal transfer sheet 7)

Except changing the coating liquid 31 for a peeling layer to a peeling layer having the following composition Except that the peeling layer was formed by the coating solution 37, the thermal transfer sheet 7 was obtained in the same manner as in the production method of the thermal transfer sheet 1.

<Coating liquid for peeling layer 37>

(Production of thermal transfer sheet A)

A thermal transfer sheet A was obtained in the same manner as in the production method of the thermal transfer sheet 1 except that the coating solution for the peeling layer 31 was changed to the coating solution O for the peeling layer having the following composition.

<Coating liquid O for peeling layer>

(Production of thermal transfer sheet B)

A thermal transfer sheet B was obtained in the same manner as in the production method of the thermal transfer sheet 1 except that the coating solution 31 for a peeling layer was changed to the coating solution P for a peeling layer having the following composition.

<Coating liquid P for peeling layer>

(Combination of transfer foil and thermal transfer sheet)

The thermal transfer sheet prepared as described above was combined with the intermediate transfer media (1) and (2) produced as described above as the transfer foil as shown in Table 3 below to form a combination of each example and each comparative example. In addition, the combination of the transfer foil and the thermal transfer sheet with the adhesion force of the transfer layer and the peeling layer under the above-mentioned "specific measurement conditions" of 0.03 N / cm or more was set as the combination of the examples, but less than 0.03 N / The combination of cm is a combination of a comparative example.

(Measurement of adhesion)

On the receiving layer of the intermediate transfer medium used as the transfer foil in the combination of Table 3 below, a sublimation-transferred photo-tone thermal transfer image was formed. Next, the thermal transfer sheet is formed so that the receiving layer of the intermediate transfer medium forming the thermal transfer image is brought into contact with the peeling layer of the thermal transfer sheet of the combination of Table 3 below, and the thermal transfer sheet is transferred using the following test printer. The transfer speed was set to 42.3 mm / sec, and the energy shown in Table 3 was applied to the back side of the thermal transfer sheet to remove the transfer layer from the intermediate transfer medium. region. When a specific area of the transfer layer is removed from the intermediate transfer medium, the transfer layer and the release layer of the intermediate transfer medium in close contact with the peeling layer are self-supporting together The tensile strength of the peeling layer at the time of peeling is in a printer, using a tensiometer (ASK-1000 model, Okura Industrial Co., Ltd.) located between the winding roller of the thermal transfer sheet and the heating means (thermal head) (Strand)), and the tensile strength was measured as the adhesion between the transfer layer and the peeling layer. Table 3 shows the measurement results of adhesion. The adhesion (N / cm) is a value obtained by dividing the value measured by the tensiometer by the width of the application area. The peeling angle of the transfer layer when the transfer layer was peeled from the support was 50 °.

(Test printer)

Average resistance of heating element: 5241 (Ω)

Printing density in main scanning direction: 300 (dpi)

Printing density in sub-scanning direction: 300 (dpi)

Line period: 2 (msec / line)

Printing start temperature: 29.0 ~ 36.0 (℃)

Pulse duty cycle: 85 (%)

Applied voltage: 18 (V) ~ 24 (V)

Transport speed: 42.3mm / sec

Application area width: 4.1846 (cm)

(Evaluation of peelability (3))

In the above-mentioned adhesion measurement, the removal condition of the transfer layer removed by the peeling layer was visually confirmed, and the peelability was evaluated based on the following evaluation criteria. The evaluation results are shown in Table 3.

"Evaluation criteria"

A ... Correctly remove the transfer layer corresponding to the "specific area".

B ... A part of the transfer layer corresponding to the "specific area" is left slightly, or the transfer layer is removed slightly beyond the "specific area", but it is not a problem in use.

C ... A part of the transfer layer corresponding to the "specific area" remains, or the transfer layer is removed in a way beyond the "specific area", but to the extent that it is not a problem in use.

NG (1) ... defective because the transfer layer corresponding to "specific area" was not removed correctly.

NG (2) ... The transfer layer corresponding to the "specific area" is not removed at all and is defective.

1‧‧‧ substrate

2‧‧‧ undercoat

4‧‧‧ stripping layer

5‧‧‧ back layer

10‧‧‧ heat transfer sheet

Claims (6)

A thermal transfer sheet characterized by a thermal transfer sheet provided with a peeling layer on a substrate. The peeling layer contains at least a vinyl chloride resin and an acrylic resin. The quality of the vinyl chloride resin is relative to the peeling layer. The total mass of the delamination is in a range of more than 50% by mass and less than 95% by mass. A thermal transfer sheet characterized by a thermal transfer sheet provided with a stripping layer on a substrate, the stripping layer containing a number average molecular weight (Mn) of 17,000 or less and a glass transition temperature (Tg) of 50 ° C or more and 120 Polyester resin below ℃. The thermal transfer sheet according to claim 2, wherein the polyester resin has a polyester resin coefficient average molecular weight (Mn) of 3500 or more and less than 9,000. The thermal transfer sheet according to claim 2 or 3, wherein the polyester-based resin-based glass-transition temperature (Tg) is a polyester-based resin having a temperature of 50 ° C or higher and 100 ° C or lower. A combination of a transfer foil and a thermal transfer sheet, characterized in that the aforementioned transfer foil is provided on a support body with a transfer layer which can be peeled from the support, and the aforementioned thermal transfer sheet is provided on a substrate It has a stripping layer on it, The transfer foil and the thermal transfer sheet are overlapped so that the transfer layer and the peeling layer face each other. The transfer speed of the thermal transfer sheet is 42.3 mm / sec, and the energy applied to the thermal transfer sheet is 0.143. In the condition of mJ / dot, the adhesion between the transfer layer and the peeling layer measured when the specific area of the transfer layer is removed by the peeling layer is 0.03 N / cm or more. For example, if the combination of the transfer foil and the thermal transfer sheet of claim 5 is applied, the energy applied to the thermal transfer sheet is changed from 0.1 mJ / dot to 0.2 mJ / dot. The adhesion force measured when the change is 0.03N. / cm or more.